EP3785281B1 - Câble électrique ignifuge - Google Patents

Câble électrique ignifuge Download PDF

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Publication number
EP3785281B1
EP3785281B1 EP18721995.1A EP18721995A EP3785281B1 EP 3785281 B1 EP3785281 B1 EP 3785281B1 EP 18721995 A EP18721995 A EP 18721995A EP 3785281 B1 EP3785281 B1 EP 3785281B1
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EP
European Patent Office
Prior art keywords
flame
polyolefin
cable
based composition
retardant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP18721995.1A
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German (de)
English (en)
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EP3785281A1 (fr
EP3785281C0 (fr
Inventor
Vito SCRIMA
Luigi Caimi
Massimo GOLA
Attilio Citterio
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Prysmian SpA
Politecnico di Milano
Original Assignee
Prysmian SpA
Politecnico di Milano
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Publication date
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Publication of EP3785281A1 publication Critical patent/EP3785281A1/fr
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Publication of EP3785281C0 publication Critical patent/EP3785281C0/fr
Publication of EP3785281B1 publication Critical patent/EP3785281B1/fr
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the present disclosure relates to a flame retardant electrical cable.
  • the present disclosure relates to a flame retardant electrical cable which exhibits reduced dripping (occurrence of droplets) from its plastic coverings when exposed to flame temperatures, e.g. in case of fire.
  • the cable according to the disclosure can be used particularly for low-voltage (LV) applications.
  • LV low-voltage
  • cables protected with fire resistant or flame-retardant layers are suitable for the strictest safety requirements in the case of fire, such as: emergency lightings, alarms and automatic fire detection systems, activation of smoke outlets or shutters, fans, air conditioning, and telephone and video surveillance systems.
  • the flame retardancy of an electric cable can be evaluated for compliance with and certified by national and/or international standards.
  • a significant role in the performance of a cable in case of fire is played by the plastic coverings, for example by the electric insulation which is usually the thickest one.
  • an important aspect of the flame-retardant performance of a cable is related to the possible occurrence of droplets when the electrical cable is exposed to flame temperatures, due to the melting of the plastic material forming the electric insulation or other coverings of the cable, and, when droplets are generated, to their amounts and to time span until the droplets end burning.
  • CPR Construction Product Regulation
  • One method for reducing dripping under fire of flame-retardant cables is to use special polymers (e.g. olefin polymers treated with phosphorous-based compositions) in the manufacture of the electrical insulation of the cable.
  • special polymers e.g. olefin polymers treated with phosphorous-based compositions
  • the use of those special polymers results in a significant increase of the production costs of the cable.
  • an insulating layer for providing a fire-resistant ceramic under fire conditions comprises:
  • the composition can be used for providing fire-resistant insulation for electric cables.
  • US 2008/0251273 discloses a plenum cable component with excellent fire-retardant properties prepared from a polyolefin-based composition comprising an olefin polymer and a metal hydroxide being surface treated with a phosphorous-based composition.
  • the plenum cable component can be an insulation layer.
  • Polymers of ethylene and vinyl silanes may be used as olefin polymer.
  • a moisture cross-linkable composition can be obtained by using a polyethylene grafted with a vinylsilane.
  • the polyolefin-based composition may contain other flame-retardants including silica, carbon nanotubes and talc.
  • CN 105367965 discloses a halogen-free flame retardant polyolefin cable ceramic material comprising 40-60 parts of ethylene-vinyl acetate copolymer, 40-60 parts of ethylene- ⁇ -olefin copolymer, 5-10 parts of high-density polyethylene resin, 5-10 parts of maleic anhydride-grafted amorphous polyolefin, 30-60 parts of mica powder, 40-60 parts of ceramic powder, 5-20 parts of calcium oxide, 2-10 parts of zinc oxide, 10-20 parts of microencapsulated red phosphorus, 40-60 parts nano aluminium hydroxide, 2-5 parts of organic montmorillonite, 2-5 parts of multi-walled carbon nanotubes, 0.5-2 parts of antioxidant and 2-8 parts of silicon lubricant masterbatch.
  • WO 2006/094250 discloses a plenum cable component prepared from a polyolefin-based composition, containing an olefinic polymer and a surface treated metal hydroxide.
  • the composition may also comprise a nanoclay.
  • US 2011240335 discloses a flame-retardant cable including at least one conductor and at least one coating made from a flame-retardant composition
  • a flame-retardant composition comprising (a) at least one crystalline propylene homopolymer or copolymer; (b) at least one copolymer of ethylene with at least one C 3 -C 12 alpha-olefin, having a density of from 0.860 to 0.904 g/cm 3 and a Molecular Weight Distribution Index not higher than 5; (c) at least one ethylene homopolymer or copolymer of ethylene with at least one C 3 -C 12 alpha-olefin having a density of from 0.905 to 0.970 g/cm3; and (d) at least one flame-retardant filler.
  • US 2015/274927 discloses a polymer composition comprising an inorganic ionomer and a ionic liquid.
  • An object of the present disclosure is providing a flame-retardant electric cable, in particular a flame-retardant electric cable for low-voltage applications, having reduced dripping (occurrence of droplets) or no dripping when exposed to flame temperatures, such as those involved in a fire, so as to meet the requirements for certification according to the current international standards, for example the standard EN 50399:2011/A1 (2016), in a class as high as possible.
  • a flame-retardant electric cable as above which should also show good mechanical properties and workability as well as suitable dielectric properties of its insulating coating.
  • an electric cable has improved flame retardant properties, particularly a reduced dripping under fire, when its conductors are coated with an insulating coating made from a flame-retardant polyolefin-based composition comprising a cross-linked polyolefin as base polymer and a balanced combination of silica and carbon nanotubes.
  • the present disclosure relates to a flame-retardant electric cable having a core comprising an electric conductor and an electrically insulating coating made from a flame-retardant polyolefin-based composition comprising:
  • the polyolefin-based composition for the cable insulating layer of the disclosure further comprises talc.
  • the polyolefin-based composition for the cable insulating layer of the disclosure further comprises talc and graphene.
  • a cable provided with an insulating coating made from a flame-retardant composition as specified above has improved flame-retardant properties, especially regarding a lower dripping or even absence of dripping during burning, which render the cable of the disclosure capable of being certified in high classes of the current international standards, for example of the Commission Delegated Regulation (EU) 2016/364 of 1 July 2015.
  • EU Commission Delegated Regulation
  • the provision of an insulating coating made from the flame-retardant polyolefin-based composition as specified above allows to impart improved flame-retardant properties to the cable without impairing its mechanical and dielectric properties as well as workability of the insulating layer for example through conventional extrusion techniques.
  • the cable according to the disclosure can be used particularly for low-voltage (LV) applications.
  • LV low-voltage
  • low voltage (LV) cable it is meant a voltage of less than about 1 kV.
  • the cable of the present disclosure is suitable to transport electric current for energy and for telecommunication.
  • Cable 10 has a core comprising a conductor 11 which is an element of elongate shape made of an electrically conductive material, e.g. aluminium, copper, carbon nanotubes or composite thereof.
  • the conductor 11 may be in the form of a solid bar or a bundle of wires, preferably stranded.
  • the core may include a single conductor or preferably a plurality of conductors.
  • Each conductor (in the case of Figure 1 , the single conductor 11) of the cable of the disclosure is electrically insulated by an insulating layer 12 in form of an extruded polymeric coating having flame-retardant properties.
  • the insulating layer is extruded in direct contact with the conductor.
  • An outer jacket 13, in extruded polymeric material such as polyethylene, may be provided to surround the insulating layer 12 and in direct contact thereof.
  • the cable insulating layer is made from a polyolefin-based composition comprising a cross-linked polyolefin as base polymer.
  • the cross-linked polyolefin of the polyolefin-based composition for the cable insulating layer of the disclosure can be a polyethylene homopolymer such as low-density polyethylene (LDPE) or very low density polyethylenes (VLDPE), or a polyethylene copolymer such as linear low-density polyethylene (LLDPE), ethylene propylene rubber (EPR) or ethylene propylene diene monomer rubber (EPDM).
  • LDPE low-density polyethylene
  • VLDPE very low density polyethylenes
  • LLDPE linear low-density polyethylene
  • EPR ethylene propylene rubber
  • EPDM ethylene propylene diene monomer rubber
  • the base polymer can be cross-linked by a silane-based crosslinking agent, such as a vinyl silane and/or by a peroxide, such as dibutyl-peroxide.
  • a silane-based crosslinking agent such as a vinyl silane
  • a peroxide such as dibutyl-peroxide
  • the polyolefin-based composition includes 5-10 wt% of silica and 0.5-2 wt% of carbon nanotubes, the percentage being referred to the weight of the polyolefin-based composition.
  • a polyolefin-based composition having the above combination of fillers in the respective amount ranges specified above has been surprisingly found to provide an electrically insulating coating with improved flame-retardant properties, particularly a reduced or no dripping during burning, without substantially impairing its dielectric and mechanical properties.
  • the silica (a.k.a. silicon dioxide) of the polyolefin-based composition for the cable insulating layer of the disclosure is amorphous silica.
  • the silica is a powder material in which the particles have a substantially spherical shape. The use of a silica being amorphous and/or made of substantially spherical particles makes the extrusion of the polyolefin-based easier.
  • the median diameter (D50) of the silica spherical particles is within the range 100-200 nm.
  • the specific surface area (as measured by BET method) can be within a range 10-30 m 2 /g.
  • carbon nanotube means any allotrope form of carbon with a cylindrical nanostructure.
  • Carbon nanotubes are members of the fullerene structural family and are categorized as single-walled nanotubes (SWCNTs) and multi-walled nanotubes (MWCTNs).
  • the carbon nanotube of the polyolefin-based composition for the cable insulating layer of the disclosure is MWCNT.
  • MWCNTs show a better fire resistance and a lower influence on the dielectric performance of the composition.
  • the polyolefin-based composition for the cable insulating layer of the disclosure comprises carbon nanotubes in an amount up to 2 wt% of the polyolefin-based composition.
  • the amount of carbon nanotubes exceeds such amount, the insulating properties of the resulting insulating coating may be worsened to an unacceptable extent due to the intrinsic electrical conductivity of carbon nanotubes.
  • the polyolefin-based composition for the cable insulating layer of the disclosure further includes talc (a.k.a. hydrated magnesium silicate, Mg 3 S 14 O 10 (OH) 2 ).
  • Talc can be added in an amount of from 2.5 wt% to 5 wt% with respect to the weight of the polyolefin-based composition. Talc helps in providing an insulating layer with smooth surface after extrusion. Also, the Applicant perceived that talc can play a role in improving the flame retardant properties of the polyolefin-based composition.
  • the total amount of talc plus silica is up to 10 wt% with respect to the weight of the polyolefin-based composition.
  • the polyolefin-based composition for the cable insulating layer of the disclosure further comprises talc and graphene.
  • graphene means any allotrope form of carbon made of a single layer of carbon atoms arranged in a hexagonal lattice. It can be in the form of nanoribbons, nanoplatelets, and nano-onions.
  • Graphene can be added in an amount up to 0.2 wt% with respect to the weight of the polyolefin-based composition.
  • graphene is used in the form of platelets.
  • graphene nanoplatelets can have an average thickness of 5-10 nm (nanometers) and varying size up to 50 um.
  • the production of the cable according to the disclosure can be carried out by conventional techniques which involves making a cross-linkable polyolefin composition including the fillers and other additives, such as a crosslinking agent, into an extruder.
  • a crosslinking agent such as a crosslinking agent
  • the resulting composition is then extruded and cross-linked.
  • the step can be carried out in a water bath, steam chamber, or at ambient conditions (ambient moisture).
  • the electric cable of the present disclosure can be used for transporting electrical energy or data.
  • the cable of the present disclosure is for transporting low-voltage (LV) electrical currents, i.e. electrical currents at a voltage equal to or lower than 1 KV.
  • LV low-voltage
  • Cables A to G Test samples of cables according to the disclosure and comparative cable (hereinafter referred to as Cables A to G) were prepared using an insulating coating comprising, respectively, the fillers and their amounts according to the present disclosure and not.
  • test cables were obtained by processing and curing cross-linkable compositions based on LLDPE copolymer containing hexene-1 as comonomer, a crosslinking system comprising vinyl trimethoxy and tert-butyl-cumyl peroxide, and one or more fillers as indicated in Table 1.
  • the flame-retardant fillers used in the compositions were:
  • Table 1 below reports the amounts of LLDPE base polymer, crosslinking system and fillers included in the cross-linkable compositions used for making the insulating coating of each of the Cables A to G, where the comparative cables are marked by an asterisk.
  • Test samples of the cables obtained according to Example 1 were subjected to tests for their dripping behaviour as well as their mechanical and dielectric properties.
  • each sample was conditioned for 16 hours at 80°C and at a relative moisture of 80%.
  • the extrusion behaviour of the test samples obtained according to Example 1 was also evaluated and is indicated as OK when the surface of the extruded insulating layer was satisfactorily smooth, or NO when it was so "rough” as to provide potential discontinuities at the interface with the cable jacket to be extruded thereupon, and X when it could be improved with extrusion tricks known to the skilled person.
  • the dielectric properties were evaluated by measuring electrical conductivity according to the standard CEI 20-34 (2001). Based on the results obtained, the dielectric properties are said as OK when suitable for an insulating layer for low voltage cable (acceptable/good) or NO when not.
  • comparative cable G - which has an insulating coating without fillers - shows mechanical and dielectric properties compliant for the intended use, but at the same time exhibits heavy dripping such that a cable comprising this insulation could be qualified as d2 according to the European standard EN 50399 at best (if the other cable layers have no worse dripping performance).
  • talc in partial replacement for silica and the presence of graphene as additional fillers in amounts within the respective ranges provided by the present disclosure results in a polyolefin-based composition for cable insulating layers having mechanical and dielectric properties that are both compliant for the intended use and, at the same, and exhibiting few dripping (Cable E according to the disclosure).
  • the observed few occurrence and persistence of flaming droplets is such that Cable E according to the disclosure could be advantageously qualified as d1 according to the European standard EN 50399 (if the other cable layers have a similar or better dripping performance).
  • the tested cable qualified to be suitable for areas with very high fire risks.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Insulating Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Insulated Conductors (AREA)

Claims (10)

  1. Câble électrique ignifuge (10) ayant une âme comprenant un conducteur électrique (11) et une couche électriquement isolante (12) faite à partir d'une composition à base de polyoléfine ignifuge comprenant :
    a) une polyoléfine réticulée en tant que polymère de base ;
    b) une silice ; et
    c) des nanotubes de carbone
    dans lequel la quantité de silice est de 5 % en poids à 10 % en poids de la composition à base de polyoléfine, et la quantité de nanotubes de carbone est de 0,5 % en poids à 2 % en poids de la composition à base de polyoléfine.
  2. Câble électrique ignifuge selon la revendication 1, dans lequel la polyoléfine réticulée de la composition à base de polyoléfine ignifuge est sélectionnée parmi un homopolymère de polyéthylène et un copolymère de polyéthylène.
  3. Câble électrique ignifuge selon la revendication 1, dans lequel la silice est une silice amorphe.
  4. Câble électrique ignifuge selon la revendication 1 ou 3, dans lequel la silice est une matière pulvérulente dans laquelle les particules présentent une forme sphérique.
  5. Câble électrique ignifuge selon la revendication 1, dans lequel les nanotubes de carbone sont des nanotubes multiparois.
  6. Câble électrique ignifuge selon la revendication 1, dans lequel la composition à base de polyoléfine comprend en outre du talc.
  7. Câble électrique ignifuge selon la revendication 6, dans lequel la quantité totale de talc plus silice va jusqu'à 10 % en poids par rapport au poids de la composition à base de polyoléfine.
  8. Câble électrique ignifuge selon la revendication 6, dans lequel la composition à base de polyoléfine comprend en outre du graphène.
  9. Câble électrique ignifuge selon la revendication 8, dans lequel la quantité de graphène dans la composition à base de polyoléfine ignifuge va jusqu'à 0,2 % en poids par rapport au poids de la composition à base de polyoléfine.
  10. Câble électrique ignifuge selon la revendication 8, dans lequel le graphène est utilisé sous forme de plaquettes.
EP18721995.1A 2018-04-26 2018-04-26 Câble électrique ignifuge Active EP3785281B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2018/060664 WO2019206412A1 (fr) 2018-04-26 2018-04-26 Câble électrique ignifuge

Publications (3)

Publication Number Publication Date
EP3785281A1 EP3785281A1 (fr) 2021-03-03
EP3785281C0 EP3785281C0 (fr) 2023-06-07
EP3785281B1 true EP3785281B1 (fr) 2023-06-07

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ID=62111047

Family Applications (1)

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EP18721995.1A Active EP3785281B1 (fr) 2018-04-26 2018-04-26 Câble électrique ignifuge

Country Status (4)

Country Link
EP (1) EP3785281B1 (fr)
AU (1) AU2018420983B2 (fr)
ES (1) ES2954249T3 (fr)
WO (1) WO2019206412A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11620810B2 (en) * 2020-11-23 2023-04-04 Corning Research & Development Corporation Identification of droplet formation during cable burn testing

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI322176B (en) 2002-10-17 2010-03-21 Polymers Australia Pty Ltd Fire resistant compositions
CN101133465B (zh) * 2005-03-03 2012-03-07 联合碳化化学及塑料技术有限责任公司 压力通风系统电缆部件和包括其的通信电缆
BRPI0823007B1 (pt) * 2008-08-05 2019-03-06 Prysmian S.P.A. Cabo retardador de chamas, e, composição retardadora de chamas
US9765196B2 (en) * 2014-02-20 2017-09-19 Rutgers, The State University Of New Jersey Inorganic ionomers made from minerals
CN105367965B (zh) * 2015-11-30 2018-09-07 中广核三角洲（苏州）高聚物有限公司 耐火电缆用无卤阻燃陶瓷化聚烯烃电缆料及其制备方法

Also Published As

Publication number Publication date
EP3785281A1 (fr) 2021-03-03
AU2018420983A1 (en) 2020-11-12
EP3785281C0 (fr) 2023-06-07
AU2018420983B2 (en) 2024-03-28
ES2954249T3 (es) 2023-11-21
WO2019206412A1 (fr) 2019-10-31
US20210241940A1 (en) 2021-08-05

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